Water soluble negative tone photoresist

ABSTRACT

A method is described for reducing the space width of holes in a first resist pattern and simultaneously removing unwanted holes to change the pattern density in the resulting second pattern. This technique provides holes with a uniform space width as small as 100 nm or less that is independent of pattern density in the second pattern. A positive resist is patterned to form holes with a first pattern density and first space width. A water soluble negative resist is coated over the first resist and selectively exposed to form a second patterned layer consisting of water insoluble plugs in unwanted holes in the first pattern and a thin water insoluble layer on the first resist pattern in unexposed portions. The plugs may form dense and isolated hole arrays while the thin insoluble layer reduces space width to the same extent in remaining holes in the second pattern.

RELATED PATENT APPLICATIONS

This application is related to the following: Docket # TS01-376, Ser.No. 10/002,986, filing date Nov. 30, 2001; Docket # TS01-463, Ser. No.10/005,806, filing date Dec. 5, 2001; Docket # TS02-162, Ser. No.10/443,359, filing date May 22, 2003; and Docket # TS02-211, Ser. No.10/268,586, filing date Oct. 10, 2002, all assigned to a commonassignee.

FIELD OF THE INVENTION

The invention relates to a method of fabricating an integrated circuitin a semiconductor device. More particularly, the present inventionrelates to a method of reducing hole or trench sizes in a photoresistpattern and for optimizing the print density of said pattern.

BACKGROUND OF THE INVENTION

Photoresist patterning is a key step in the formation of integratedcircuits in semiconductor devices. A photoresist, hereafter referred toas resist, is typically spin coated on a substrate, baked to form afilm, and patternwise exposed by employing an exposure tool and a maskthat contains a device pattern. Radiation is transmitted throughtransparent regions of the mask to selectively expose portions of theresist layer. The resist layer is developed in a media such as anaqueous base solution to produce a resist pattern on the substrate. Eachtechnology generation or node in the microelectronics industry isassociated with a particular minimum feature size in the resist pattern.As technology advances have been continuous in recent years, the minimumfeature size requirement has rapidly shifted from 250 nm to 180 nm andthen to 130 nm. New products are now being developed for a sub-100 nmtechnology node.

Some of the more common features that are printed in resist layers arecontact or via holes and trenches which have a variety of pitches. InFIG. 1, a resist layer 2 is patterned on a substrate 1. In one region ofthe pattern, a pitch P1 is equal to the space width W1 of a feature suchas hole 3 a and the distance D1 separating hole 3 a from an adjacenthole 3 b. Another region of the pattern has a pitch P2 consisting of aspace width W1 in a hole 3 c and a distance D2 between hole 3 c and anadjacent hole 3 d. The ratio D1/D2 may vary from slightly more than 1 toa number as high as 10 or more. One of the problems associated with atypical patterning process is that space width W1 is dependent onpattern density. For example, space width W1 in an opening like hole 3 cthat is part of a dense array is printed at a different size than spacewidth W1 for a semi-isolated hole 3 a or an isolated hole in the samepattern even though the space width on the mask used to print thepattern is the same for all of the holes 3 a-3 d. As a result, opticalproximity corrections (OPC) are required on the mask design that willenable the lithography process to print dense and isolated holes withequal space widths W1. OPC can be cumbersome to generate and a period ofone or two months may be necessary before a new mask with OPCcorrections is available. It is desirable to have an alternative methodin which the pattern density in a resist pattern is adjusted so thatholes 3 a-3 d are all printed with the same space width W1.

The minimum resolution that can be achieved in a printed pattern isdefined by the equation R=kλ/NA where R is the minimum feature size thatcan be resolved, k is a constant, λ is the exposure wavelength, and NAis the numerical aperture of the exposure tool. While exposure toolshaving mercury lamps that emit g-line (436 nm) or i-line (365 nm)radiation have been widely used in the industry, the trend in newertechnologies is to move to shorter wavelengths such as 248 nm from KrFexcimer lasers or 193 nm from ArF excimer lasers to achieve smallerfeature sizes approaching 100 nm. In the near future, 157 nm radiationfrom F₂ lasers and 13 to 14 nm wavelengths from extreme ultravioletradiation (EUV) sources will be available for printing sub-100 nmfeatures. Projection electron beam (e-beam) tools are also beingdeveloped for sub-100 nm applications.

A method of forming smaller contact holes by a double exposure processdescribed in U.S. Pat. No. 5,573,634 may be applied to any UV wavelengthsince it lowers the amount of diffracted light from a single exposure.The technique avoids exposing adjacent holes on a single mask whichproduces a significant background intensity between the holes in theaerial image that reaches the resist layer.

Commercial resist compositions are available in two general types thatare referred to as positive tone and negative tone formulations. Inpositive tone or positive resist, exposed regions become soluble in adeveloper solution that is typically an aqueous base. Unexposed regionsin the film stay insoluble in the developer and remain on the substrate.For negative resists, exposed regions become insoluble in a developerwhile the unexposed regions remain soluble and are washed away. Theresist solution is spin coated on a substrate and baked to form a filmthickness that may vary from about 0.2 microns to several microns. As ageneral rule, the thickness is about 3 or 4 times the size of theminimum space width or line width. Therefore, to print a 100 nm contacthole, a 300 to 400 nm thick film is typically applied in order to have apatterning process latitude that is manufacturable.

Most state of the art positive and negative resists operate by achemical amplification mechanism in which a photosensitive componentabsorbs energy from the exposing radiation and generates a strong acid.One acid molecule is capable of removing many polymer protecting groupsin a positive resist mechanism or initiating several crosslinkingreactions in a negative resist mechanism. A post-exposure bake isusually required to drive the reaction to completion within a fewminutes so that the process is compatible with a high throughputmanufacturing scheme. Chemically amplified (CA) resists are especiallyuseful with Deep UV (248 nm) radiation or with sub-200 nm exposurewavelengths. Another important feature of a CA resist is that inaddition to a polymer, solvent, and photoacid generator component, theCA resist also contains a quencher which is usually a base such as anamine that controls acid diffusion in the exposed film and acts as anacid scavenger in the resist solution.

The negative resist imaging process may involve a crosslinking mechanismor a polarity change to render the exposed regions insoluble indeveloper. Crosslinking occurs when a photo generated acid catalyzesbond formation between two polymer chains or between a polymer and anadditive containing reactive groups. Depending on the molecular weight(MW) of the original polymers, a few crosslinks are all that might beneeded to convert a soluble polymer into an insoluble network ofpolymers. This solubility difference is the basis for forming a patternin an exposed negative tone film.

Traditionally, resists have been formulated in organic solvents, butrecently water based formulations that are more environmentallycompatible have been developed. U.S. Pat. No. 5,017,461 describes awater soluble negative tone composition based on a polyvinyl alcohol(PVA) and an acid generator that is a diazonium salt. An hydroxyl groupon the polymer reacts with the diazonium salt to form an ether andliberate nitrogen and HCl. When the film is heated, HCl induces thepolymer to lose a molecule of water and form an alkene that is insolublein water developer. This is an example of a negative resist based on apolarity change.

Another water soluble negative resist that does not rely on acrosslinking mechanism is provided in U.S. Pat. No. 5,998,092. Aphotoacid reacts with an acetal group on a polymer side chain to producea B-keto acid that loses CO₂ to form a polymer which is insoluble inaqueous base developer. This composition is especially useful inavoiding swelling in aqueous developer.

A water soluble resist that is compatible with a crosslinking mechanismis described in U.S. Pat. No. 5,948,592 in which a calcium salt of anorganic acid is added to an aqueous form of casein, a photosensitivematerial, and optionally, a crosslinker. An acetate, lactate, or formatesalt is used to improve photosensitivity, resolution, and etchresistance in a resist pattern that may be hardened by baking from 150°C. to 300° C.

Individual components of negative resists have been developed thatpossess water solubility as an added property. For example, a watersoluble sugar is claimed as an improved crosslinker in related U.S. Pat.Nos. 5,532,113 and 5,536,616. This crosslinker is used in combinationwith a p-hydroxystyrene polymer and a triphenylsulfonium salt that arenot soluble in water and have an optical absorbance that is mostsuitable for 248 nm exposures. The pattern is developed in aqueous base.In U.S. Pat. No. 5,648,196, a water soluble photoacid generator (PAG) isdescribed and is formulated with a p-hydroxystyrene polymer and a watersoluble sugar. Either water or aqueous base developer is acceptable. ThePAG is preferably a dimethylarylsulfonium salt wherein the aryl grouphas one or more hydroxy substituents.

Still another crosslinking formulation is provided in U.S. Pat. No.5,858,620 in which a water soluble polymer and crosslinker are coated ona patterned layer containing acid that has a hole with a space width ofabout 400 nm. The patterned layer is either baked at 150° C. to causeacid diffusion that induces crosslinking in the water soluble layer orthe patterned resist is exposed and baked to drive acid into the toplayer. In either case, a crosslinked coating is formed on the patternedresist that effectively shrinks the space width to about 300 nm. Inrelated art, U.S. Pat. No. 6,319,853 describes a crosslinking mechanismto shrink a 200 nm space to a 110 nm space width. However, thecrosslinking layer does not contain a quencher and the extent of aciddiffusion is determined by only the bake temperature and time which maybe difficult to reproduce uniformly across a wafer.

Therefore, a improved method that offers a higher degree of control inshrinking space widths which is desirable for new technologies involvinghole patterns with space widths approaching 130 nm or smaller is needed.A process that is able to shrink space widths of holes in addition toadjusting pattern density is especially appealing to manufacturing sinceit provides more flexibility in the overall scheme of fabricatingsemiconductor devices.

SUMMARY OF THE INVENTION

One objective of the present invention is to provide a method ofoptimizing print density in a resist pattern.

A further objective of the present invention is to provide a method ofshrinking the space width of a hole or trench that has been patterned byUV radiation including sub-200 nm wavelengths or by e-beam exposurewhere the space width has a size that can be as small as 130 nm or less.

A still further objective of the present invention is to provide amethod for adjusting a resist pattern print density that is compatiblewith chemically amplified resists and conditions for processing theseresists.

Yet another objective of the present invention is to provide a negativetone resist that may be coated over an existing photoresist pattern tosimultaneously adjust the print density in the pattern and shrink thespace width of holes or trenches in the pattern.

These objectives are achieved in one embodiment with a lithographyprocess that involves a first mask pattern for printing fine holes ortrenches in a resist. The mask may be an attenuated phase shifting mask(att-PSM), an alternating PSM (alt-PSM), or a binary mask and thelithography process may include resolution enhancement techniques suchas off-axis illumination and scattering bars in the mask design. Apositive resist layer is preferably coated on a substrate and is exposedby 248 nm, 193 nm, 157 nm, or EUV radiation followed by a post-exposebake and development in an aqueous base. Optionally, e-beam exposure isused to form the first patterned resist layer. The first patternedresist layer has holes with a first space width and a first patterndensity.

A second resist layer comprised of a water soluble negative resist iscoated over the first patterned resist layer. The negative resist isexposed with radiation through a second mask pattern to form crosslinkedregions in the negative resist in unwanted holes in the first patternedresist layer. The so called unwanted holes will be eliminated during asubsequent pattern transfer step that will reduce the pattern density ofthe resulting pattern in the substrate. During the post-expose bake(PEB) step, residual acid in the first patterned resist layer diffusesinto adjacent regions including unexposed regions of the negative resistand induces a crosslinking reaction that produces a thin crosslinkedlayer on the first patterned resist layer. In addition, furthercrosslinking occurs in the crosslinked regions formed by the negativeresist exposure to generate crosslinked plugs in unwanted holes of thefirst patterned layer. The negative resist is then developed with awater or aqueous base solution to produce plugs in unwanted holes of thefirst patterned resist layer and a thin crosslinked layer over theremaining portion of the first patterned layer.

The second patterned layer comprised of the thin crosslinked layer andthe crosslinked plugs has holes with a second space width that is lessthan the first space width in the first patterned layer. The thincrosslinked layer effectively shrinks the size of unplugged holes in thefirst patterned resist layer by forming a liner on the sidewalls of theunplugged holes. The thickness of the thin crosslinked layer andtherefore the second space width may be controlled by the amount ofquencher in the negative resist and the PEB conditions. The secondpatterned layer serves as an etch mask while the hole pattern in thesecond patterned layer is transferred into the substrate. The patterndensity is adjusted since the crosslinked plugs prevent unwanted holesfrom being transferred into the substrate during the etch step. Thefirst patterned resist layer and the second patterned resist layer arestripped and the substrate is ready for subsequent processing.

The invention also encompasses a novel negative tone water solublephotoresist that is particularly useful as the negative resist describedin the first embodiment. In a preferred composition, the negative resistis comprised of a water/isopropanol (IPA) solvent mixture, apoly(vinylacetal), ethyleneurea as crosslinker, a photoacid generator(PAG) that may be a water soluble onium salt, a triazine, animidosulfonate, or a diazonium sulfonate, and a quencher that ispreferably an amine or a nitrogen containing compound. The PAGpreferably generates a strong acid such as a sulfonic acid upon exposureto one or more wavelengths in the range of from about 10 nm to about 300nm. The strong acid catalyzes a chemical amplification mechanism so thatthe exposure dose is low enough for a high throughput lithographicprocess. The PAG should also be thermally stable during processing ofthe negative resist and should not react with the quencher while insolution or in the unexposed resist film. The quencher is preferably acompound or salt that will not bake out of the spin coated negativeresist film during bake processes. A ratio of PAG to quencher in theformulation is employed that will enable a low exposure dose but stillallow acid diffusion into unexposed regions to be controlled. The amountof each component in the negative resist is typically optimized toprovide a pattern that has vertical sidewalls and a good exposure andfocus latitude during the patterning step.

In a second embodiment, a hole or trench pattern is formed in a firstpatterned resist layer according to a method described in the firstembodiment. The first patterned resist layer has holes with a firstspace width and a first pattern density. A water soluble negative resistconsisting of a polymer having polar functionality such as hydroxygroups, a PAG, a water based solvent, and a quencher is coated over thepatterned layer. The negative resist is exposed with radiation through asecond mask pattern that causes a reversal in polymer polarity in thenegative resist within unwanted holes in the first patterned resistlayer. During the post-expose bake (PEB) step, residual acid in thefirst patterned resist layer diffuses into adjacent regions includingunexposed regions of the negative resist and induces a reaction thatgenerates a non-polar polymer. As a result a thin layer of waterinsoluble negative resist with a non-polar polymer is formed on thefirst patterned layer. In addition, the acid formed by the negativeresist exposure causes a further reaction within unwanted holes of thefirst patterned layer and produces water insoluble plugs with a polymerof reversed polarity.

The remaining water soluble negative resist layer is then removed bydeveloping with a water solution to produce a second patterned resistlayer comprised of water insoluble plugs in unwanted holes of the firstpatterned resist layer and a thin water insoluble negative resist with apolymer of reversed polarity on the remaining portion of the firstpatterned resist layer. The second patterned resist layer has holes witha second space width that is less than the first space width in thefirst patterned layer.

The second patterned resist layer effectively shrinks the size ofunplugged holes in the first patterned resist layer by forming a lineron the sidewalls of the unplugged holes. The thickness of the secondpatterned resist layer and therefore the second space width can becontrolled by the amount of quencher in the water soluble negativeresist and the PEB conditions. The second patterned resist layer servesas an etch mask while the hole pattern in the second patterned resistlayer is transferred into the substrate. The pattern density is adjustedsince the water insoluble plugs prevent unwanted holes from beingtransferred into the substrate during the etch step. The first patternedresist layer and the second patterned resist layer are stripped and thesubstrate is ready for subsequent processing.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross sectional view of a pattern that shows a resistpattern having different pitches at different locations on a substrate.

FIGS. 2-5 are cross-sectional views of various process stepsillustrating one embodiment of the present invention in which the spacewidth and pattern density of holes in a first resist pattern are reducedin a second pattern formed in a substrate.

FIGS. 6-9 are cross-sectional views showing various steps of a secondembodiment of the present invention in which the space width and patterndensity of holes in a first resist pattern are reduced in a secondpattern formed in a substrate.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is described with reference to the drawings whichare not necessarily drawn to scale and are provided by way of exampleand not intended to limit the scope of the invention. In the firstembodiment as illustrated in FIGS. 2-5, a method is described forshrinking the space width of holes in a resist pattern whilesimultaneously reducing the pattern density of the holes in the pattern.This method allows holes with the same space width but different patterndensities to be formed in a pattern in a resist layer that istransferred into a substrate. The holes may be vias, contact holes,trenches, or other features which have a space width to be decreased anda pattern density to be reduced.

Referring to FIG. 2, a substrate 10 is provided that may contain activeand passive devices in a substructure that is not shown in order tosimply the drawing and direct attention to the present invention. In oneembodiment, an anti-reflective coating or ARC (not shown) is formed onsubstrate 10 in order to control reflectivity during a subsequent resistpatterning process. The ARC may be an inorganic material such as siliconnitride or silicon oxynitride that is deposited by a chemical vapordeposition (CVD) process or the like or the ARC may be an organic layerthat is obtained by spin coating and baking a commercially availablesolution. Alternatively, an ARC may be omitted and a resist layer iscoated directly on the substrate in the next step.

A positive tone resist from a commercial supplier is spin coated andbaked to form a first resist layer 11 which normally has a thickness inthe range of about 2000 to 10000 Angstroms. The thickness is usuallydetermined by the minimum feature size in the device pattern to beprinted in the first resist layer 11. However, the thickness of thefirst resist layer 11 is also influenced by the etch rate ratio of firstresist layer 11 to substrate 10 and the depth to which a hole in asubsequently formed resist pattern is etch transferred into substrate 10in a later step represented in FIG. 5. As a general rule, the thicknessof a resist layer is about 3 to 4 times the size of the minimum spacewidth in the resulting resist pattern which in this embodiment is thespace width W₂ of holes 12 a-12 f in the first patterned resist layer11.

The selection of an appropriate resist composition to form the firstresist layer 11 depends on the dimension of the smallest feature to beprinted in the first resist layer. A Deep UV resist that is exposed witha single wavelength (248 nm) from an excimer laser or with a broadband(240-260 nm) source is preferred for printing features such as holeshaving a space width from about 130 nm to about 300 nm while a so called193 nm resist is exposed with a 193 nm wavelength from an ArF excimerlaser to print features with a space width from about 100 nm to about130 nm. An i-line resist that is exposed with a 365 nm wavelength isgenerally employed for forming patterns when the minimum space width isgreater than approximately 300 nm. Although the drawings for thisembodiment depict a single layer imaging scheme, it should be understoodthat a bilayer or trilayer scheme having a positive tone resist as thetop layer is also included within the scope of this invention.

The first resist layer 11 is exposed through a first mask (not shown)that transmits an aerial image which projects a hole pattern on thefirst resist layer 11. The first mask may be an Att-PSM or Alt-PSM, oran Att-PSM, Alt-PSM, or binary mask with scattering bars to increase theprocess window of the patterning method. Radiation from an exposuresource (not shown) passes through transparent regions of the mask toexpose selected regions of the first resist layer 11. Although 193 nm,248 nm, and 365 nm exposure tools are preferred for most currentlithography applications, it is understood that any exposure wavelengthin the range from 10 nm to about 600 nm is included in the scope of thisinvention. Optionally, an electron beam exposure tool can be used toform a pattern in the first resist layer 11. This e-beam process mayinvolve a direct write technique or a projection e-beam tool.

In a preferred embodiment when the exposure involves Deep UV or sub-200nm wavelengths, the first resist layer 11 is a chemically amplifiedresist and a post exposure bake (PEB) at temperatures from about 90° C.to 150° C. is performed following exposure to accelerate an acidcatalyzed reaction. A developer that is typically an aqueous basesolution is applied to substrate 10 to form a first patterned layer 11with holes 12 a-12 f having a space width W₂ and separated by a distanceW₃ where the ratio W₃/W₂ may vary from approximately 1 for a highpattern density to a number of about 10 or more for a low patterndensity. Patterns with intermediate W₃/W₂ ratios are referred to assemi-dense or semi-isolated.

In many applications, it is desirable to print holes with the same spacewidth but with different pattern densities. In prior art methods when asingle mask having holes of equal space width is used to print a patternwith different pattern densities, isolated holes (low pattern density)are usually printed with a smaller space width than dense arrays ofholes (high pattern density). In the present invention, holes with equalspace width are printed with a first pattern density in a first resistlayer and then unwanted (dummy) holes are removed so that the remainingholes in a second pattern in a second resist layer which are transferredinto a substrate have equal space widths but different patterndensities. Furthermore, a smaller space width may be achieved in theholes formed in the substrate than in a conventional process where apattern is a single resist layer that is subsequently etch transferredinto the substrate.

With the usual method of generating two or more pattern densities fromone exposure as shown in FIG. 1, the space width W₁ varies. OPCcorrections are often applied in prior art to adjust various portions ofthe mask pattern to enable a more uniform space width W₁ in the resistpattern. In some cases the mask compensation is not possible because ofspace constraints in the mask design or because of other complicatingfactors. The method of this embodiment is particularly useful forgenerating a more uniform space width in holes that have differentpattern densities without the need for OPC.

Referring to FIG. 2, the holes 12 a-12 f are formed with the same spacewidth W₂ in a first patterned resist layer 11 where they are separatedby a constant distance W₃ and have a first pattern density. It isunderstood that the pattern may be further comprised of other regions(not shown) having holes with a space width W_(X) that are separatedfrom one another by a distance W_(Y) where W_(X) may or may not be equalto W₂ and W_(Y) may or may not be equal to W₃. In one embodiment, W₃/W₂may be about 1 so that holes 12 a-12 f are in a dense array with a highpattern density. As mentioned previously, there may be arrays of holes(not shown) in other regions having a space width W_(X). The method ofthis embodiment provides a means of reducing all space widths W₂ andW_(X) by a constant amount while reducing the pattern density of holesin selected regions that may or may not include W_(X). Alternatively,holes 12 a-12 f may be part of a semi-dense or isolated array whereW₃/W₂ is significantly greater than 1.

In the first embodiment, the pattern density of a region 18 a thatincludes holes 12 a, 12 b and the pattern density of a region 18 c withholes 12 e, 12 f will be reduced by removing holes 12 b, 12 e in asecond patterned layer that will be subsequently be formed over thefirst patterned layer 11. Meanwhile, the pattern density of a region 18b with holes 12 c, 12 d will remain unchanged after a second patternedlayer is formed. Note that a region is defined as a portion of thesubstrate 10 and layers overlying that portion of substrate. From atop-down view (not shown), a region has a width and a length andcomprises an area as small as approximately 1 square micron to as largeas hundreds of square microns. Furthermore, a first region may have adifferent area than a second region. Those skilled in the art willappreciate an alternative embodiment wherein a plurality of regions eachwith a plurality of holes may be present in a first patterned resistlayer 11 on the substrate 10. To simplify the drawings, only threeregions with two holes in each region are shown in the first embodiment.

In FIG. 3, a water soluble negative resist comprised of a polymer, acrosslinker, photoacid generator (PAG), and a quencher which istypically a non-nucleophilic base such as an amine or a nitrogencontaining compound is coated on the first patterned resist layer 11 andbaked to form a water soluble negative resist layer 13. One particularformulation that is preferably employed to form the water solublenegative resist layer 13 is comprised of a water/IPA solvent with 4% to8% by weight of poly(vinylacetal), 0.5% to 2% by weight of ethyleneureaas crosslinker, 0.01% to 0.1% by weight of a PAG, and 1 to 30 ppm of aquencher. The preferred polymer which is a poly(vinylacetal) has thefollowing structure:

wherein R is an alkyl group and n indicates the degree ofpolymerization.

The preferred crosslinker in the water soluble negative resist isethyleneurea which has the structure:

but other ureas and water soluble crosslinkers such as glycoluril shownbelow may be used in th formulation.

An appropriate PAG is selected to function at any of the exposurewavelengths mentioned previously that include 365 nm, 248 nm, 193 nm,157 nm, and 13 to 14 nm (EUV). PAGs that are sensitive to opticalwavelengths are also sensitive to e-beam exposure. The PAG preferablygenerates a strong acid such as a sulfonic acid upon exposure whichcatalyzes a chemical amplification mechanism so that the exposure doseis low enough for a high throughput lithographic process. The PAG shouldalso be thermally stable during processing of the negative resist andshould not react with the quencher while in solution or in the unexposedresist film. In some cases, especially for 365 nm exposures, asensitizer may be added to absorb energy from the exposing radiation andthen transfer energy to the PAG. The PAG may be a water soluble oniumsalt, a triazine, an imidosulfonate, or a diazonium sulfonate, forexample.

The quencher is usually an amine or contains a basic nitrogen moietythat does not react with the polymer or PAG but traps trace amounts ofacid that might cause unwanted reactions while the resist is stored as awater solution. Appropriate quenchers depend on the PAG and polymercomposition. Furthermore, the quencher is preferably a compound or saltthat will not bake out of the coated resist film during bake processesand limits acid diffusion in the resist film. A ratio of PAG to quencherin the formulation is employed that will enable a low exposure dose butstill allow acid diffusion into unexposed regions to be controlled. Theamount of each component in the negative resist is typically optimizedto provide a pattern that has vertical sidewalls and a good exposure andfocus latitude.

The water soluble negative resist is preferably spin coated from a watersolution and does not mix with first patterned resist layer 11 duringthe coating and baking operations to form the water soluble negativeresist layer 13. The water soluble negative resist layer 13 is baked ata temperature in the range of about 80° C. to 150° C. in order to drythe film after spin coating and is then exposed through a second mask14. In one embodiment, the second mask 14 is a binary mask comprised ofa pattern that includes primarily opaque regions 15 and smalltransparent regions 16 corresponding to locations of the unwanted holes12 b, 12 e in FIG. 3. The second mask 14 may be further comprised ofscattering bars to improve the resolution and process window of thepatterning step. Alternatively, the second mask 14 is an att-PSM oralt-PSM in which the region 15 transmits light that is 180° out of phasewith light transmitted through the region 16. Although 193 nm, 248 nm,and 365 nm exposure tools are preferred for most current lithographyapplications, it is understood that any wavelength 17 in the range from10 nm to about 600 nm may be used for this step. Furthermore, theexposure may include a resolution enhancement technique (RET) such asoff-axis illumination to increase the process window of the patterningstep.

Referring to FIG. 4, the water soluble negative resist layer 13 iscrosslinked in exposed regions and following a PEB step and treatmentwith a water or aqueous base developer is transformed into a crosslinkedplug 13 a. The PAG generates a strong acid in exposed areas whichcatalyzes a reaction between the polymer and crosslinker to form acrosslinked network that is no longer soluble in water. Therefore, whena developer is applied to the substrate 10 following the PEB step, onlyregions of the negative resist layer 13 that have not been crosslinkedare removed. A thin crosslinked layer 13 b is formed because residualacid in the first patterned resist layer 11 diffuses into adjacentregions of the water soluble resist layer 13 during the PEB step toinduce a crosslinking reaction. The quencher loading in the watersoluble negative resist layer 13 may be adjusted downward if a greaterthickness of the thin crosslinked layer 13 b is desired or the quencherconcentration is increased if a smaller thickness of the thincrosslinked layer 13 b is required. PEB time and temperature may also bechanged to control the thickness of the thin crosslinked layer 13 bwhich determines the amount of shrinkage in holes 12 a, 12 c, 12 d, 12f.

A second patterned layer comprised of the crosslinked plugs 13 a and thethin crosslinked layer 13 b is thereby formed on the first patternedlayer 11. The thickness of the thin crosslinked layer 13 b on horizontalsurfaces of the first patterned resist layer 11 is assumed to be equalto the thickness of the thin crosslinked layer on the vertical sidewallsof holes 12 a, 12 c, 12 d, and 12 f. The presence of the thincrosslinked layer 13 b forms a second space width W₄ in the holes 12 a,12 c, 12 d, 12 f that is less than W₂ and may not be attainable by asingle conventional patterning technique.

Note that the width of the crosslinked plug 13 a is larger than thefirst space width W₂ in the holes 12 b, 12 e to allow for some error inthe overlay of the negative resist pattern on the first patterned resistlayer 11. Therefore, it is not necessary to use the same wavelength ofradiation 17 for exposing the water soluble negative tone resist layer13 as was employed for exposing the first resist layer 11. Generally, amore economical method is to use a longer exposing wavelength for thesecond exposure, if possible. For instance, a 193 nm wavelength might beused to pattern the first resist layer 11 to form holes 12 a-12 fbetween 100 and 130 nm in space width W₂ while a 248 nm wavelength maybe employed for exposing the water soluble negative resist layer 13 toform crosslinked plugs 13 a that are between about 130 nm and 250 nm inwidth.

The pattern density in regions 18 a, 18 c has been reduced by one holeper region by forming the second patterned layer with crosslinked plugs13 a in unwanted holes 12 b, 12 e. In an alternative embodiment where aplurality of holes are formed per region in the first patterned resistlayer 11, more than one unwanted hole may be removed per region byforming a plurality of crosslinked plugs in a second patterned layerthat overlies the first patterned resist layer 11. In an embodimentwhere at least two of the regions having a plurality of holes also havethe same size and the same number of holes (equal pattern densities) inthe first patterned resist layer 11, then a different number of unwantedholes must be removed (plugged) in the two regions to form at least twodifferent pattern densities in the second patterned layer. Those skilledin the art recognize that a variety of options exist in which differentnumbers of unwanted holes may be plugged in each of the plurality ofregions.

An advantage over prior art is that all the holes 12 a, 12 c, 12 d, 12 fhave the same reduced space width W₄ whereas in conventional methods,the isolated holes 12 a, 12 f have a different size W₄ than the denseholes 12 c, 12 d.

Referring to FIG. 5, the substrate 10 is then anisotropically etched byan appropriate plasma etch method which is determined by the compositionof the substrate 10 and is well known to those skilled in the art. Thesecond patterned resist layer comprised of the crosslinked plugs 13 aand the thin crosslinked layer 13 b function as an etch mask for thetransfer of the hole pattern into substrate 10. In an embodiment wherethe etch breaks through the thin crosslinked layer 13 b, the firstpatterned resist layer serves as an etch mask. Once the pattern havingthe second pattern density has been etched to an appropriate depth intothe substrate 10, the remaining first patterned resist layer 11, thethin crosslinked layer 13 b, and crosslinked plugs 13 a are stripped bya conventional method. The holes 12 b, 12 e are not formed in thesubstrate 10 because the crosslinked plugs 13 a block the plasma etch.

As a result of the etch step, the holes 12 a, 12 c, 12 d, 12 f in thesubstrate 10 have a space width W₄ that has been reduced from W₂ in thefirst patterned resist layer 11. In addition, the pattern density inregions 18 a, 18 c has been reduced while the pattern density remainsthe same in the region 18 b. Therefore, a pattern has been produced inthe substrate 10 in which the holes 12 a, 12 c, 12 d, 12 f have the samereduced space width but region 18 a and region 18 c have a differentpattern density than the region 18 b. Note that other holes (not shown)in the first patterned resist layer 11 with a space width W_(X) that isequal to or different than W₂ will also shrink by an amount equal to(W₂-W₄). Optionally, the second mask for exposing the water solublenegative resist layer 13 may be designed to remove unwanted holes (notshown) in other regions with a space W_(X) unequal to W₂. In otherwords, the second mask may have a pattern with holes of one space widthto remove unwanted holes in the first patterned resist layer 11 with aspace width W₂ and the second mask may have holes of another space widthto remove unwanted holes in the first patterned layer having a spacewidth W_(X).

A method has thus been demonstrated whereby holes may be selectivelyremoved in a first patterned layer by forming a second patterned layeron the first patterned layer. The pattern in the second patterned layeris transferred into a substrate to decrease the pattern density in atleast one of the regions of the substrate while simultaneously reducingthe space width of all the remaining holes. The method also anticipatesthe use of phase shifting masks and resolution enhancement techniques toprovide higher resolution and a larger process window in the patterningprocess. Furthermore, the method is not limited by the space width of ahole in the first patterned layer and can be applied to plug holes assmall as 130 nm or less. Moreover, the method of this invention is moreversatile than prior art methods that only reduce the space width in anopening or only adjust the pattern density in a resist layer.

In a second embodiment illustrated in FIGS. 6-9, a method is describedthat relates to shrinking the space width of holes in at least tworegions of a first resist pattern having equal pattern densities andequal space widths whereby a second pattern is formed in a substrate inwhich the two regions have holes with different pattern densities butequal and smaller space widths. In other words, a reduced patterndensity is formed in at least one of the substrate regions and all holesformed in the substrate have reduced space widths compared to the firstresist pattern.

Referring to FIG. 6, a substrate 20 is provided that is typicallycomprised of silicon and may contain active and passive devices in asubstructure that is not shown in order to simply the drawing. Ananti-reflective coating (ARC) 21 is formed on the substrate 20 in orderto control reflectivity during a subsequent resist patterning process.The ARC 21 may be an inorganic material such as silicon nitride orsilicon oxynitride that is deposited by a CVD process or the like or theARC may be an organic layer that is obtained by spin coating and bakinga commercially available ARC solution.

A positive tone resist is spin coated on ARC 21 and baked to form afirst resist layer 22 which normally has a thickness in the range ofabout 2000 to 10000 Angstroms. The resist thickness is usuallydetermined by the minimum feature size in the device pattern to beprinted in the first resist layer 22 as is appreciated by those whopractice the art. The type of first resist layer 22 selected alsodepends on the dimension of the smallest feature to be printed by thelithographic process as described in the first embodiment.

The first resist layer 22 is exposed through a first mask (not shown)comprised of a hole pattern that projects an aerial image on the firstresist layer 22. The holes may be vias, contact holes, trenches, orother openings used in the art. The mask may be an Att-PSM or Alt-PSM,or an Att-PSM, Alt-PSM, or binary mask with scattering bars to increasethe process window of the patterning method. Radiation from an exposuresource (not shown) passes through transparent regions of the mask toexpose selected regions of the first resist layer 22. Although 193 nm,248 nm, and 365 nm exposure tools are preferred for most currentlithography applications, it is understood that any exposure wavelengthin the range from 10 nm to about 600 nm is included in the scope of thisinvention. Optionally, an e-beam exposure tool that may involve a directwrite technique or a projection method may be used to form a pattern infirst resist layer 22.

In the embodiment where the exposure involves Deep UV or sub-200 nmwavelengths, the first resist layer 22 is a preferably a chemicallyamplified resist and a PEB at temperatures from about 90° C. to 150° C.is performed following exposure to accelerate an acid catalyzedreaction. The substrate 20 is then developed with water or an aqueousbase solution to form a first patterned resist layer 22 with holes 23a-23 f having a width W₇ and separated by a distance W₆ where the ratioW₆/W₇ may vary from approximately 1 for a high pattern density to anumber of 10 or more for a low pattern density. Patterns withintermediate W₆/W₇ ratios are referred to as semi-dense orsemi-isolated.

In many applications, it is desirable to print holes with the same spacewidth but with different pattern densities. In prior art methods when asingle mask having holes of equal space width is used to print a patternwith different pattern densities, isolated holes (low pattern density)are usually printed with a smaller space width than dense arrays ofholes (high pattern density). In the present invention, holes with equalspace width are printed with a first pattern density in a first resistlayer and then unwanted (dummy) holes are removed so that the remainingholes in a second pattern in a second resist layer which are transferredinto a substrate have equal space widths but different patterndensities. The method of this embodiment is particularly useful forgenerating a more uniform space width in holes that have differentpattern densities without the need for OPC.

Referring to FIG. 6, the holes 23 a-23 f are formed with the same spacewidth W₇ in a first patterned resist layer 22 where they are separatedby a constant distance W₆ and have a first pattern density. It isunderstood that the pattern may be further comprised of other regions(not shown) having holes with a space width W_(X) that are separatedfrom one another by a distance W_(Y) where W_(X) may or may not be equalto W₇ and W_(Y) may or may not be equal to W₆. In one embodiment, W₆/W₇may be about 1 so that the holes 23 a-23 f are in a dense array with ahigh pattern density. The method of this embodiment provides a means ofreducing all space widths W₇ and W_(X) by a constant amount whilereducing the pattern density of holes in selected regions that may ormay not include W_(X). Alternatively, the holes 23 a-23 f may be part ofa semi-dense or isolated array where W₆/W₇ is significantly greater than1.

In the second embodiment, the pattern density of a first region 29 thatincludes the holes 23 a, 23 b, 23 c will be reduced by removing theholes 23 b, 23 c in a second patterned layer that will be subsequentlybe formed over the first patterned resist layer 22. Meanwhile, thepattern density of a second region 30 with the holes 23 d, 23 e, 23 fwill remain unchanged after a second patterned layer is formed. Notethat a region is defined as a portion of the substrate 20 and layersoverlying that portion of substrate. From a top-down view (not shown), aregion has a width and a length and comprises an area as small asapproximately 1 square micron to as large as hundreds of square microns.Furthermore, a first region may have a different area than a secondregion. Those skilled in the art will appreciate an alternativeembodiment wherein a plurality of regions each with a plurality of holesmay be present in a first patterned resist layer 22 on the substrate 20.To simplify the drawings, only two regions with three holes in eachregion are shown in the second embodiment.

In FIG. 7, a water soluble negative resist is coated on the firstpatterned resist layer 22 and baked to form water soluble negativeresist layer 24. The negative resist solution is typically comprised ofa water solvent, a polymer having polar functionality such as an hydroxygroup, a PAG, and preferably has a quencher which is usually anon-nucleophilic base such as an amine or a nitrogen containing compoundthat controls acid diffusion in the exposed resist film and acts as anacid scavenger to prevent acid catalyzed reactions from occurring in theresist solution. The polymer is further characterized as having a polargroup that undergoes an acid catalyzed rearrangement or an acid inducedcleavage such that the resulting polymer is no longer soluble in water.Such polymers and water soluble negative resists are known in prior artand examples thereof are included in the compositions described earlierin U.S. Pat. Nos. 5,998,092 and 5,017,461. Since the water solublenegative resist layer 24 is coated from a water solution, it does notmix with the first patterned resist layer 22 during the coating andbaking operation above.

The water soluble negative resist layer 24 is baked at a temperature inthe range of about 80° C. to 150° C. in order to dry the film after spincoating and is then exposed through a second mask 25. In one embodiment,the second mask 25 is a binary mask that comprised of a pattern thatincludes primarily opaque regions 26 and small transparent regions 27corresponding to locations of the unwanted holes 23 b, 23 c in FIG. 6.The second mask 25 may be further comprised of scattering bars toimprove resolution and the process window of the patterning step.Alternatively, the second mask 25 is an att-PSM or alt-PSM in which theregion 26 transmits light that is 180° out of phase with lighttransmitted through the region 27. Although 193 nm, 248 nm, and 365 nmexposure tools are preferred for most current lithography applications,it is understood that any wavelength 28 in the range from 10 nm to about600 nm may be used for this step. Furthermore, the exposure may includeresolution enhancement techniques such as off-axis illumination toincrease the process window of the patterning step.

Referring to FIG. 8, the polymer in the water soluble negative resistlayer 24 is transformed in exposed regions during the exposure andpost-expose baking step to produce a water insoluble resist plug 24 a.The PAG generates a strong acid in exposed areas which catalyzes acleavage or rearrangement within the polymer to produce a polymerproduct that is non-polar and which is no longer soluble in water.Therefore, when an aqueous or isopropanol/water developer is applied tothe substrate 20 following a post-expose bake, only regions of the watersoluble negative resist layer 24 that have unreacted polymer areremoved. A thin water insoluble layer 24 b is formed because residualacid in the first patterned resist layer 22 diffuses into adjacentregions of the water soluble negative resist layer 24 during the PEBstep to induce a cleavage or rearrangement that changes the polymerpolarity from polar to non-polar. The quencher loading of the watersoluble negative resist layer 24 may be adjusted downward if a largerthickness of the thin water insoluble layer 24 b is desired or upward ifa smaller thickness of the thin water insoluble layer 24 b is required.PEB time and temperature may also be changed to control the thickness ofthe thin water insoluble layer 24 b which determines the amount ofshrinkage in the holes 23 a, 23 d, 23 e, 23 f.

A second patterned layer comprised of the water insoluble plugs 24 a andthe thin water insoluble layer 24 b is thereby formed on the firstpatterned resist layer 22. The thickness of the thin water insolublelayer 24 b on horizontal surfaces of the first patterned resist layer 22is assumed to be equal to the thickness of the thin water insolublelayer on the vertical sidewalls of the holes 23 a, 23 d, 23 e, and 23 f.The presence of the thin water insoluble layer 24 b forms a second spacewidth W₈ in the holes 23 a, 23 d, 23 e, 23 f that is less than W₇ andmay not be attainable by a single conventional patterning technique.

Note that the width of the water insoluble plug 24 a is larger than thefirst space width W₇ of holes 23 b, 23 c to allow for some error in theoverlay of the negative resist pattern in the second mask 25 on thefirst patterned resist layer 22. Therefore, it is not necessary to usethe same wavelength of radiation 28 for exposing the water solublenegative tone resist layer 24 as was employed for exposing the firstresist layer 22. Generally, a more economical method is to use a longerexposing wavelength for the second exposure, if possible. For instance,a 193 nm wavelength might be used to pattern the first resist layer 22to form holes 23 a-23 f between 100 and 130 nm in space width W₇ while a248 nm wavelength may be employed for exposing the water solublenegative resist layer 24 to form the water insoluble plugs 24 a that maybe between 130 nm and 250 nm in width.

The pattern density in the region 29 has been reduced by two holes byforming the second patterned layer with the water insoluble plugs 24 ain the unwanted holes 23 b, 23 c. In an alternative embodiment where aplurality of holes are formed per region in the first patterned resistlayer 22, only one hole or a plurality of holes may be removed perregion by forming an appropriate number of water insoluble plugs in asecond patterned layer that overlies the first patterned resist layer22. In an embodiment where at least two of the regions having aplurality of holes also have the same size and the same number of holes(equal pattern densities) in the first patterned resist layer 22, then adifferent number of unwanted holes must be removed (plugged) in the tworegions to form at least two different pattern densities in the secondpatterned layer. Those skilled in the art recognize that a variety ofoptions exist in which different numbers of unwanted holes may beplugged in each of the plurality of regions. An advantage over prior artis that all the holes 23 a, 23 d, 23 e, 23 f have the same reduced spacewidth W₈ whereas in conventional methods, an isolated hole 23 a has adifferent size W₈ than the dense holes 23 d, 23 e, 23 f.

Referring to FIG. 9, an ARC 21 open step is then performed with a plasmaetch that typically involves oxygen if the ARC 21 is an organic layer.The etch removes the ARC 21 exposed by the holes 23 a, 23 d, 23 e, 23 fand stops on the substrate 20. The substrate 20 is then anisotropicallyetched by an appropriate plasma etch method known to those skilled inthe art. The second patterned resist layer comprised of the waterinsoluble plugs 24 a and the thin water insoluble layer 24 b function asan etch mask for the transfer of the hole pattern into the substrate 20.In an embodiment where the etch breaks through the thin water insolublelayer 24 b, the first patterned resist layer 22 serves as an etch mask.Once the pattern having the second pattern density has been etched to anappropriate depth into the substrate 20, the remaining first patternedresist layer 22, the thin water insoluble layer 24 b, water insolubleplugs 24 a, and the ARC 21 are stripped by a conventional method such asa wet stripper or oxygen ashing. The holes 23 b, 23 c are not formed inthe substrate 20 because the water insoluble plugs 24 a block the plasmaetch.

As a result of the etch step to transfer the pattern in the secondpatterned layer into the substrate 20, the holes 23 a, 23 d, 23 e, 23 fin the substrate 20 have a space width W₈ that has been reduced from W₇in the first patterned resist layer 22. In addition, the pattern densityin the region 29 has been reduced while the pattern density remains thesame in the region 30. Therefore, a pattern has been produced in thesubstrate 20 in which the holes 23 a, 23 d, 23 e, 23 f have the samereduced space width but the region 29 has a different pattern densitythan the region 30. Note that other holes (not shown) in the firstpatterned resist layer 22 with a space width W_(X) that is equal to ordifferent than W₇ will also shrink by an amount equal to (W₇-W₈).Optionally, the second mask for exposing the water soluble negativeresist layer 24 may be designed to remove unwanted holes (not shown) inother regions with a space W_(X) unequal to W₇. In other words, thesecond mask may have a pattern with holes of one space width to removeunwanted holes in the first patterned resist layer 22 with a space widthW₇ and the second mask may have holes of another space width to removeunwanted holes in the first patterned layer having a space width W_(X).

A method has thus been demonstrated whereby holes may be selectivelyremoved in a first patterned resist layer by forming a second patternedlayer on the first patterned resist layer. The pattern in the secondpatterned layer is transferred into a substrate to decrease the patterndensity in at least one of the regions of the substrate whilesimultaneously reducing the space width of all the remaining holes. Themethod also anticipates the use of phase shifting masks and resolutionenhancement techniques to provide higher resolution and a larger processwindow in the patterning process. Furthermore, the method is not limitedby the space width of a hole in the first patterned layer and may beapplied to plug holes as small as 130 nm or less. Moreover, the methodof this invention is more versatile than prior art methods that onlyreduce the space width in an opening or only adjust the pattern densityin a resist layer.

While this invention has been particularly shown and described withreference to, the preferred embodiment thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade without departing from the spirit and scope of this invention.

1. A method for manufacturing a microelectronic structure comprising: (a) forming a first patterned resist layer comprised of holes having a first region and a second region on a substrate, said holes have a first pattern density and a first space width; (b) forming a water soluble negative resist layer on said first patterned resist layer that fills the holes in the first patterned resist layer; (c) patternwise exposing said water soluble negative resist layer through a mask to selectively expose portions of said water soluble negative resist layer within and adjacent to selected holes in said first patterned resist layer; (d) post-expose baking said substrate to form crosslinked plugs in exposed portions of said water soluble negative resist layer, said crosslinked plugs fill selected holes in said first patterned resist layer, and to form a thin crosslinked negative resist layer in unexposed regions of said water soluble negative resist layer adjacent to the first patterned resist layer, (e) removing non-crosslinked regions of said water soluble negative resist layer by applying a developer solution to form a second patterned layer comprised of the crosslinked plugs and the thin crosslinked negative resist layer wherein the second patterned layer has holes with a second space width that is smaller than said first space width and a pattern density in the first region that is different than the pattern density in the second region; and (f) transferring the pattern in said second patterned layer into said substrate.
 2. The method of claim 1 wherein forming said first patterned resist layer comprises the steps of patternwise exposing a positive tone resist through a mask with one or more wavelengths of radiation in a range of about 10 nm to 600 nm or with e-beam exposure and developing the exposed positive resist with a developer solution.
 3. The method of claim 1 wherein the first patterned resist layer contains a residual amount of acid that diffuses into adjacent unexposed regions of the water soluble negative resist layer and catalyzes a crosslinking reaction during the post-expose baking step to form the thin crosslinked negative resist layer.
 4. The method of claim 1 wherein said water soluble negative resist layer is formed from a solution comprised of a water/isopropanol solvent containing about 4 to 8 weight % of poly(vinylacetal), about 0.5 to 2 weight % of ethylene urea as a crosslinker, about 0.01 to 0.1 weight % of a photoacid generator, and about 1 to 30 ppm of a quencher.
 5. The method of claim 1 wherein said water soluble negative resist is exposed with one or more wavelengths of radiation in a range of about 10 nm to 600 nm.
 6. The method of claim 1 wherein said crosslinked plug has a larger width than the first space width of the holes in said first patterned resist layer.
 7. The method of claim 4 wherein the amount of quencher is adjusted to produce a different thickness of the thin crosslinked negative resist layer.
 8. The method of claim 1 further comprised of forming an anti-reflective coating (ARC) on the substrate prior to forming said first patterned resist layer.
 9. The method of claim 2 wherein the masks used for forming the first patterned resist layer and for exposing the water soluble negative resist layer are selected from a group including binary masks, attenuated phase shifting masks, and alternating phase shifting masks.
 10. The method of claim 2 wherein the patternwise exposing step of the positive resist layer and the water soluble negative resist layer involve resolution enhancement techniques including off-axis illumination and a mask with scattering bars.
 11. The method of claim 1 wherein said developer solution for removing the non-crosslinked portions of the water soluble negative resist layer comprises a water solution or an aqueous base solution.
 12. The method of claim 1 wherein transferring the pattern in said second patterned layer comprises a plasma etch process.
 13. The method of claim 1 wherein the holes are contact holes, vias, or trenches.
 14. A method of reducing a space width and a pattern density in a resist pattern on a substrate, comprising: (a) providing a substrate with a first patterned resist layer comprised of holes formed thereon, said substrate having a first region and a second region and said holes have a first pattern density and a first space width; (b) forming a water soluble negative resist layer on the first patterned resist-layer that fills the holes in the first patterned resist layer; (c) patternwise exposing said water soluble negative resist layer through a mask to selectively expose portions of said water soluble negative resist layer within and adjacent to selected holes in said first patterned resist layer; (d) post-expose baking said substrate to form crosslinked plugs in exposed portions of said water soluble negative resist layer, said crosslinked plugs fill selected holes in said first patterned resist layer, and to form a thin crosslinked negative resist layer in unexposed regions of said water soluble negative resist layer adjacent to the first patterned resist layer, and (e) removing non-crosslinked regions of said water soluble negative resist layer by applying a developer solution to form a second patterned layer comprised of the crosslinked plugs and the thin crosslinked negative resist layer wherein the second patterned layer has holes with a second space width that is smaller than said first space width and a pattern density in the first region that is different than the pattern density in the second region.
 15. The method of claim 14 wherein forming said first patterned resist layer comprises the steps of patternwise exposing a positive tone resist through a mask with one or more wavelengths of radiation in a range of about 10 nm to 600 nm or with e-beam exposure and developing the exposed positive resist with a developer solution.
 16. The method of claim 14 wherein the first patterned resist layer contains a residual amount of acid that diffuses into adjacent unexposed regions of the water soluble negative resist layer and catalyzes a crosslinking reaction during the post-expose baking step to form the thin crosslinked negative resist layer.
 17. The method of claim 14 wherein said negative resist layer is formed from a solution comprised of a water/isopropanol solvent containing about 4 to 8% of poly(vinylacetal), about 0.5 to 2% of ethylene urea as a crosslinker, about 0.01 to 0.1% of a photoacid generator, and about 1 to 30 ppm of a quencher.
 18. The method of claim 14 wherein said negative resist is exposed with one or more wavelengths of radiation in a range of about 10 nm to 600 nm.
 19. The method of claim 14 wherein said crosslinked plug has a larger width than the first width of the holes in said first patterned resist layer.
 20. The method of claim 17 wherein the amount of quencher is adjusted to produce a different thickness of the thin crosslinked negative resist layer.
 21. The method of claim 14 wherein an anti-reflective coating (ARC) is formed on the substrate prior to forming said first patterned resist layer.
 22. The method of claim 21 wherein an ARC has a refractive index (n and k values) that is selected to optimize the process of forming a first patterned resist layer on said substrate.
 23. The method of claim 15 wherein the masks used for forming the first patterned resist layer and for exposing the water soluble negative resist layer are selected from a group including binary masks, attenuated phase shifting masks, and alternating phase shifting masks.
 24. The method of claim 15 wherein the patternwise exposing step of the positive resist layer and the water soluble negative resist layer involve resolution enhancement techniques including off-axis illumination and a mask with scattering bars.
 25. The method of claim 14 wherein said first patterned layer is further comprised of a third region having holes with a first space width and a pattern density unequal to the first pattern density and wherein the second patterned layer reduces the first space width to a second space width in the third region but does not change the pattern density in the third region.
 26. The method of claim 14 wherein said substrate is comprised of a plurality of regions and the first patterned layer has a plurality of holes in each region.
 27. The method of claim 14 wherein the first patterned layer in the first and second regions of the substrate is comprised of dense holes and the second patterned layer is comprised of an isolated hole in the first region and dense holes in the second region.
 28. A method of reducing a space width and a pattern density in a resist pattern, comprising: (a) providing a substrate with a first patterned resist layer comprised of holes formed on an ARC layer, said substrate having a first region and a second region and said holes have a first pattern density and a first space width; (b) forming a water soluble negative resist layer comprised of a polar polymer on the first patterned resist layer; (c) patternwise exposing said water soluble negative resist layer through a mask to selectively expose portions of said water soluble negative resist layer within and adjacent to selected holes in said first patterned resist layer; (d) post-expose baking said substrate to form water insoluble plugs in exposed portions of said water soluble negative resist layer, said water insoluble plugs fill selected holes in said first patterned resist layer, and to form a thin water insoluble negative resist layer in unexposed regions of said water soluble negative resist layer adjacent to the first patterned resist layer, and (e) removing the remaining water soluble portions of said water soluble negative resist layer by applying a developer solution to form a second patterned layer comprised of the water insoluble plugs and the thin water insoluble negative resist layer wherein the second patterned layer has holes with a second space width that is smaller than said first space width and a pattern density in the first region that is different than the pattern density in the second region.
 29. The method of claim 28 wherein forming said first patterned resist layer comprises the steps of patternwise exposing a positive tone resist through a mask with one or more wavelengths of radiation in a range of about 10 nm to 600 nm or with e-beam exposure and developing the exposed positive resist with a developer solution.
 30. The method of claim 28 wherein the first patterned resist layer contains a residual amount of acid that diffuses into adjacent unexposed regions of the water soluble negative resist layer during the post-bake step and catalyzes a reaction that converts a water soluble polymer to a non-polar polymer that is insoluble in water to form the thin water insoluble negative resist layer.
 31. The method of claim 28 wherein said water soluble negative resist layer contains a quencher to control acid diffusion during the post expose bake step.
 32. The method of claim 28 wherein said water soluble negative resist is exposed with one or more wavelengths of radiation in a range of about 10 nm to 600 nm.
 33. The method of claim 28 wherein said water insoluble plug has a larger width than the first width of the holes in said first patterned resist layer.
 34. The method of claim 31 wherein the amount of quencher is adjusted to produce a different thickness of the thin water insoluble negative resist layer.
 35. The method of claim 28 further comprised of etching through the ARC layer at the bottom of the holes formed in the second patterned layer and performing a plasma etch to transfer the pattern in the second patterned layer into said substrate.
 36. The method of claim 29 wherein the masks used for forming the first patterned resist layer and for exposing the water soluble negative resist layer are selected from a group including binary masks, attenuated phase shifting masks, and alternating phase shifting masks.
 37. The method of claim 29 wherein the patternwise exposing step of the positive resist layer and the water soluble negative resist layer involve resolution enhancement techniques including off-axis illumination and a mask with scattering bars.
 38. The method of claim 28 wherein said substrate is comprised of a plurality of regions and the first patterned layer has a plurality of holes with a first space width in each region and wherein the holes in said second patterned layer have a second space width in the plurality of regions.
 39. The method of claim 28 wherein the first patterned layer in the first and second regions of the substrate is comprised of dense holes and the second patterned layer is comprised of an isolated hole in the first region and dense holes in the second region.
 40. A water soluble negative resist composition, said composition comprising: (a) a polymer containing vinylacetal groups; (b) an ethyleneurea crosslinker; (c) a photoacid generator; and (d) a quencher.
 41. The water soluble negative resist composition of claim 40 wherein the photoacid generator is selected from the group consisting of onium salts, imidosulfonates, and diazoketone sulfonates.
 42. The water soluble negative resist composition of claim 40 wherein the solvent is further comprised of isopropanol.
 43. The water soluble negative resist composition of claim 40 wherein the quencher is selected from a group consisting of amines, nitrogen containing compounds and derivatives thereof.
 44. The composition of claim 40 wherein the composition is comprised of about 90 to 95 parts of a water/isopropanol mixture, about 4 to 8 parts poly(vinylacetal), about 0.5 to 2 parts ethyleneurea, about 0.01 to 0.1 parts photoacid generator, and about 1 to 30 ppm of a quencher.
 45. The water soluble negative resist composition of claim 40 which is spin coated to form a negative resist layer on a substrate that is patterned by a process comprising exposure with one or more wavelengths of radiation in a range of about 10 nm to 600 nm or with electron beam exposure.
 46. The water soluble negative resist composition of claim 45 that does not mix with an underlying patterned resist layer comprised of a positive tone composition. 